Sodium metasilicate as cold-end additive

ABSTRACT

This invention is directed to a method of reducing the amount of sulfur trioxide condensation on, and therefore the amount of sulfuric acid corrosion of, metal parts at the cold-end of a combustion system and in contact with combustion gases derived from the combustion of sulfur-containing fuel, said method comprising adding to the combustion gases an effective amount for the purpose of sodium metasilicate.

This application is a continuation-in-part of application Ser. No. 713,747 filed Aug. 12, 1976 now abandoned.

DISCLOSURE OF THE INVENTION

As is well-known to boiler operators, sulfur-containing fuels present problems not only from a pollutional point of view, i.e., acid smut, but also with respect to the life and operability of metallic equipment and parts which are in contact with the flue gases containing the sulfur by-products of combustion.

Upon combustion, the sulfur in the fuel is converted to sulfur dioxide and sulfur trioxide. When sulfur trioxide reaches its dew temperature, it reacts with moisture in the flue gas to produce the very corrosive sulfuric acid. The gases themselves are troublesome as air pollutants, while the acid formed is damaging from corrosion aspects.

As can be appreciated, the greater the sulfur content of the fuel, the more the effects are harmful. This is particularly the case in industrial and utility operations where low grade oils are used for combustion purposes.

Although many additives have been utilized for the purpose of conditioning flue gases, few additives have found overall success. The reason for the relatively little success in this area is felt to be the peculiarities found in the different combustion systems and boiler designs. The gas dynamics and the loads produced, sometimes make chemical treatments for the most part impractical, therefore, requiring a combination of mechanical and chemical treatment.

The basic area to which the present invention is directed is often referred to in the industry as the "cold-end" of a boiler operation. This area is generalized as being the path in the boiler system that the combustion gases follow after the gases have, in fact, performed their service of heating water, producing steam and/or superheating steam.

In the larger boiler systems, the last stages through which the hot combustion gases flow include the economizer, the air heater, the collection equipment or the electrostatic precipitator, and then the stack through which the gases are discharged.

The present invention is drawn to the present inventor's discovery of sodium metasilicate as a cold-end additive.

It was determined that if sodium metasilicate, preferably in liquid droplet form, is fed to the moving combustion gases upstream of the cold-end surfaces to be treated and, preferably, at a point where the gases are undergoing turbulence the chemical will travel along with the gases and deposit on the downstream cold-end surfaces. The liquid droplet form of the additive is accomplished by making an aqueous solution thereof. When fed as liquid droplets the additive travels along with the combustion gases as fine solids and/or liquid droplets and deposits on the downstream cold-end surfaces. The additive could also be fed in particulate form (as dry powder), for example, as disclosed in U.S. Pat. No. 3,932,588. The deposition of the additive on the cold-end surfaces results from the transition of the gas flow from a zone of relative turbulence to a zone where the turbulence subsides or from the impact of additive on the surfaces which interrupt or restrict gas flow.

As already noted, the additive is preferably fed in liquid droplet form to the gases. There are numerous methods available to the artisan for feeding the additive in droplet form, which methods are deemed well within the skill of the art. For example, liquid atomizer nozzles could be utilized for the purpose. The present inventor obtained satisfactory results using a sonic feed nozzle to produce a mist of the additive solution even though additive deposits formed on the nozzle. The use of a pressure atomizing nozzle system with in-line dilution and water purging should resolve any problems related to the formation of deposits on the nozzle. The size range of the liquid droplets is preferably small enough to ensure that the additive will be carried along with the combustion gases so as to be deposited on the surfaces to be treated. Based upon the present inventor's prior experience in this area, the size of the droplets could be as large as about 360 microns with the preferred maximum size being about 260 microns. The same size limitations would apply to particle sizes if the additive is present in particulate form. The amount of the sodium metasilicate added is a function of the sulfur content of the fuel, and more specifically, the SO₃ (sulfur trioxide) produced upon combustion. On an actives basis, as little as about 0.15 pound of sodium metasilicate per pound of SO₃ generated could be used. The preferred minimum is about 0.25 pound of sodium metasilicate per pound of SO₃. Based on economic considerations, the amount of active additive fed could be as high as about 1.0 pound per pound of SO₃, while about 0.75 pound of sodium metasilicate per pound of SO₃ represents the preferred maximum. Particularly good results were observed at a feed rate of 0.45 pound per pound of SO₃.

At the point of adding the additive (point of addition) the combustion gases have a temperature of from about 250° F. to about 1000° F. and preferably from about 350° F. to about 650° F. Since, in most instances, the temperature of the combustion gases will be at least 405° F. at the point of addition, that is the most preferred lower limit of the temperature range.

In order to assess the efficacy of the inventive compound various tests were conducted on industrial boiler systems which were fired by fuel oil containing about 2.2 percent sulfur. The abilities of the inventive additive to coat surfaces and to reduce acid deposition, corrosion and fouling were evaluated. Acid deposition rates at various surface temperatures were determined by titrating washings from a standard air-cooled CERL probe. The nature of the surface coating was determined by visual inspection of the probe. The washings were also analyzed for total iron and total solids content to obtain indications of corrosion rates and fouling tendencies, respectively. Using a Land meter, the rate of acid build-up (RBU) was determined.

The material tested was an aqueous solution containing 25% active sodium metasilicate. While the anhydrous form of sodium metasilicate was used, the hydrated form could also be used. The additive, in liquid form, was fed to the combustion gases in a duct at the cold-end of the systems, using an atomizer nozzle located in the duct.

In a first series of tests, which will hereinafter be referred to as the preliminary tests, the combustion gases contained about 18 parts of sulfur trioxide per million parts of combustion gases on a volume basis.

In a second series of tests, which will hereinafter be referred to as the confirming tests, the combustion gases contained about 55 parts of sulfur trioxide per million parts of combustion gases on a volume basis. In the confirming tests the additive was further diluted with one part water by volume.

EXAMPLE 1

As already noted, the effects of the inventive additive on acid deposition rates at various surface temperatures were determined by titrating washings from a probe similar to a standard British Central Electricity Research Laboratories (CERL) acid deposition probe. The construction and operation of this probe as well known in the art as evidenced by an article entitled "An Air-cooled Probe for Measuring Acid Deposition in Boiler Flue Gases" by P. A. Alexander, R. S. Fielder, P. J. Jackson, and E. Raask, page 31, Volume 38, Journal of the Institute of Fuel; which is hereby incorporated by reference to indicate the state of the art. Washings from the probe were titrated for sulfuric acid with sodium hydroxide.

The results of these tests are reported in Tables 1A and 1B below in terms of acid deposition rate expressed as milliliters of 0.01N NaOH needed to titrate one fourth the amount of acid which deposited on 18.8 square inches (in²) to the phenolphthalein end point. The feedrates reported are expressed as pounds of active additive per hour, and the steam loads reported are also expressed as pounds per hour. The % O₂ reported is the oxygen content of the combustion gases on a % volume basis. Table 1A contains the results of the preliminary tests, and Table 1B contains the results of the confirming tests. In the preliminary tests, the acid deposition rates at 220° F. were determined; while in the confirming tests, the determinations were for acid deposition at 230° F. and 250° F. In the preliminary tests, the probe was exposed to the combustion gases for thirty minutes; while in the confirming tests, the probe was exposed for the time periods indicated.

                  TABLE 1A                                                         ______________________________________                                                Feedrate Steam Load       Acid Deposition                               Additive                                                                              (pph)    (pph × 10.sup.3)                                                                    % O.sub.2                                                                            220° F                                 ______________________________________                                         None   --       75-76      2.3-3.0                                                                              8.5                                           None   --       90         2.7   10.0                                          Na.sub.2 SiO.sub.3                                                                    4.1      90         2.7   0                                             Na.sub.2 SiO.sub.3                                                                    4.1      90         2.7   0                                             ______________________________________                                    

                  TABLE 1B                                                         ______________________________________                                         Ex-        Feed-   Steam                                                       posure     rate    Load            Acid Deposition                             Additive                                                                              (hours) (pph)   (pph×10.sup.3)                                                                   % O.sub.2                                                                            230° F                                                                        250° F                       ______________________________________                                         None   0.5     --      100     2.5-3.0                                                                              38    28                                  None   0.5     --      100     2.5-3.0                                                                              38    28                                  None   0.5     --      114     2.5-3.0                                                                              46    32                                  None   3.0     --      104     2.5-3.0                                                                              108   72                                  Na.sub.2 SiO.sub.3                                                                    0.5     3.8     100     2.5-3.0                                                                              15    12                                  Na.sub.2 SiO.sub.3                                                                    0.5     3.8     114     2.5-3.0                                                                              25    20                                  Na.sub.2 SiO.sub.3                                                                    3.0     3.8     104     2.5-3.0                                                                              52    42                                  ______________________________________                                    

From the results reported in Tables 1A and 1B it can be seen that the rate of acid deposition on the probe was reduced significantly when the sodium metasilicate was added to the combustion gases. This reduction in the acid deposition rate reflects the efficacy of the additive as a neutralizing agent.

EXAMPLE 2

In a second series of tests, the efficacy of the inventive additive with respect to lowering the apparent acid dew point in the cold-end of the boiler system was evaluated. Using a commercially available Land dew point meter, the condensation of a conducting film of sulfuric acid on a controlled temperature probe tip was detected by the onset of the flow of electric current between electrodes embedded in the tip. This permitted the determination of the apparent acid dew point, and comparative rates of acid build-up directly on probe surfaces were obtainable from the rate of increase in current with time at any tip temperature. The results of these tests are reported in Tables 2A and 2B below. The feedrate of active additive and the boiler steam load are both expressed as pounds per hour, the apparent dew points are expressed as degrees Farenheit (° F.) and the rates of acid build-up (RBU) are expressed as micro-amperes per minute μ amp min ⁻¹). Table 2A contains the results of the preliminary tests, and Table 2B contains the results of the confirming tests. The rate of acid build-up was determined only for a portion of the tests as indicated in the tables and was determined at a probe surface temperature of 230° F. for both tests. A reported RBU range indicates that the RBU changed during the test. Apparent acid dew point is defined as that temperature at which an acid film contacts a surface, at the cold-end in this instance.

                  TABLE 2A                                                         ______________________________________                                                Feedrate Steam Load        Dew Point                                    Additive                                                                              (pph)    (pph × 10.sup.3)                                                                     % O.sub.2                                                                            (° F)                                                                           RBU                                  ______________________________________                                         None   --       88          2.6   279     120                                  Na.sub.2 SiO.sub.3                                                                    4.1      88          2.6   262      70                                  ______________________________________                                    

                  TABLE 2B                                                         ______________________________________                                                                           Dew                                                 Feedrate Steam Load        Point                                        Additive                                                                              (pph)    (pph × 10.sup.3)                                                                     % O.sub.2                                                                            (° F)                                                                        RBU                                     ______________________________________                                         None   --       114         2.5-3.0                                                                              293  400                                     None   --       116         2.5-3.0                                                                              300  420-560                                 None   --       124         2.5-3.0                                                                              296  --                                      None   --       124         2.5-3.0                                                                              300  --                                      None   --       125         2.5-3.0                                                                              296  280-500                                 Na.sub.2 SiO.sub.3                                                                    3.8      114         2.5-3.0                                                                              165  0                                       Na.sub.2 SiO.sub.3                                                                    3.8      124         2.5-3.0                                                                              160  0                                       ______________________________________                                    

From Tables 2A and 2B it can be seen that the sodium metasilicate demonstrated efficacy both with respect to lowering the apparent acid dew point in the cold-end and with respect to decreasing the rate of acid build-up directly on surfaces in the cold-end. By lowering the apparent acid dew point, the chance of the acid condensing in the cold-end of the boiler system at a given temperature is decreased. Furthermore, by lowering the apparent acid dew point in the cold-end, the combustion gas temperature can be lowered, resulting in an increase in boiler efficiency without a corresponding increase in corrosion of surfaces at the cold-end.

EXAMPLE 3

Using a portion of the washings obtained from the CERL probe described in Example 1 above, the efficacy of the inventive additive with respect to protecting cold-end surfaces against corrosion was evaluated. Since the iron (Fe) content of the washings indicated the amount of corrosion of the test surfaces exposed to combustion gases, comparisons of the iron content of the washings provided a method of evaluating the efficacy of the sodium metasilicate. The results of these comparative tests are reported below in Tables 3A and 3B, with Table 3A containing the results of the preliminary tests and Table 3B containing the results of the confirming tests. In the preliminary tests, the probe was exposed to the combustion gases for 0.5 hour, and in the confirming tests the probe was exposed for the periods as indicated in Table 3B. The steam loads and active additive are expressed as pounds per hour (pph), the oxygen content of the combustion gases as percent oxygen (%O₂) by volume, and the iron content as parts of iron per million parts of washing liquid at the probe temperatures indicated.

                  TABLE 3A                                                         ______________________________________                                         Feedrate     Steam Load           Iron (ppm)                                   Additive                                                                              (pph)     (pph × 10.sup.3)                                                                     % O.sub.2                                                                            230° F                                                                        250° F                         ______________________________________                                         None   --        90          2.7   16    6                                     Na.sub.2 SiO.sub.3                                                                    4.1       90          2.7   8     4                                     Na.sub.2 SiO.sub.3                                                                    4.1       90          2.7   8     5                                     ______________________________________                                    

                  TABLE 3B                                                         ______________________________________                                         Ex-        Feed-   Steam                                                       posure     rate    Load            Iron (ppm)                                  Additive                                                                              (hours) (pph)   (pph×10.sup.3)                                                                   % O.sub.2                                                                            230° F                                                                        250° F                       ______________________________________                                         None   0.5     --      100     2.5-3.0                                                                              70    55                                  None   0.5     --      100     2.5-3.0                                                                              90    60                                  None   0.5     --      100     2.5   60    25                                  None   3.0     --      104     2.5-3.0                                                                              130   70                                  None   6.0     --      104     2.6-3.1                                                                              400   200                                 Na.sub.2 SiO.sub.3                                                                    0.5     3.8     100     2.5-3.0                                                                              32    16                                  Na.sub.2 SiO.sub.3                                                                    3.0     3.8     104     2.5-3.0                                                                              35    35                                  Na.sub.2 SiO.sub.3                                                                    6.0     3.8     104     2.5-3.0                                                                              80    30                                  ______________________________________                                    

From the results reported in Tables 3A and 3B, it can be seen that the corrosion was indeed effectively reduced; and these results are seen to indicate the efficacy of the additive in reducing the corrosion of surfaces exposed to combustion gases in the cold-end of a boiler system.

EXAMPLE 4

In addition to analyzing the washings from the CERL probe for iron content, the total solids content of each sample was also determined to evaluate the fouling tendencies of the sodium metasilicate. While it is expected that an additive treatment at the cold-end of a boiler system would cause fouling, the fouling should not be so severe as to outweigh the advantages of the cold-end additive. The results of these tests are reported below in Tables 4A and 4B. In each of the preliminary tests, the results of which are reported in Table 4A, the probe was exposed to the combustion gases for a period of 0.5 hour; while in each of the confirming tests, the results of which are reported in Table 4B, the probe was exposed for a time period as indicated. The total solids are reported as parts of total solids per million parts of washing water at the probe surface temperatures indicated.

                  TABLE 4A                                                         ______________________________________                                         Feed-      Steam                                                               rate       Load              Total Solids (ppm)                                Additive                                                                              (pph)   (pph×10.sup.3)                                                                     % O.sub.2                                                                            230° F                                                                        250° F                                                                        300° F                       ______________________________________                                         None   --      90        2.7   180   130    70                                 Na.sub.2 SiO.sub.3                                                                    4.1     90        2.7   540   520   500                                 Na.sub.2 SiO.sub.3                                                                    4.1     90        2.7   600   570   540                                 ______________________________________                                    

                                      TABLE 4B                                     __________________________________________________________________________     Exposure  Feedrate                                                                            Steam Load  Total Solids (ppm)                                  Additive                                                                            (hours)                                                                             (pph)                                                                               (pph×10.sup.3)                                                                   % O.sub.2                                                                          230° F                                                                      250° F                                                                      300° F                               __________________________________________________________________________     None 0.5  --   100     2.5-3.0                                                                             570                                                                                390                                                                               300                                         None 3.0  --   104     2.5-3.0                                                                            1800                                                                               1300                                                                               150                                         None 6.0  --   104     2.6-3.1                                                                            3000                                                                               2000                                                                               400                                         Na.sub.2 SiO.sub.3                                                                  0.5  3.8  100     2.5-3.0                                                                             550                                                                                520                                                                               425                                         Na.sub.2 SiO.sub.3                                                                  3.0  3.8  104     2.5-3.0                                                                            2600                                                                               2500                                                                               2100                                        Na.sub.2 SiO.sub.3                                                                  6.0  3.8  104     2.5-3.0                                                                            5200                                                                               5000                                                                               4800                                        __________________________________________________________________________

Based upon the results reported in Tables 4A and 4B, the rate of solids deposition on the surfaces when the additive is used is considered to be acceptable, particularly since the deposits were easily removed.

EXAMPLE 5

In another series of tests, the CERL probe was exposed to the combustion gases for various periods of time, removed and visually inspected. The results are reported below in Table 5. The sodium metasilicate solution was further diluted with one part of water by volume.

                  TABLE 5                                                          ______________________________________                                                Exposure                                                                Additive                                                                              (hours)  Appearance of Probe                                            ______________________________________                                         None   0.5      Green coating on cold-end of probe.                            None   3.0      Heavy green coating on cold-end.                               None   6.0      Very heavy green coating on cold-end,                                          which coating was difficult to wash off.                       Na.sub.2 SiO.sub.3                                                                    0.5      Gritty white deposit.                                          Na.sub.2 SiO.sub.3                                                                    3.0      Moderate white deposit on leading                                              and trailing edge. Deposits were                                               easily removed.                                                Na.sub.2 SiO.sub.3                                                                    6.0      Same as 3 hours, but with more                                                 deposit.                                                       ______________________________________                                     

Having thus described the invention, what is claimed is:
 1. A method of reducing the amount of sulfur trioxide condensation on, and therefore the amount of sulfuric acid corrosion of, metal parts at the cold-end of a combustion system in contact with combustion gases derived from the combustion of sulfur-containing fuel, which combustion gases flow along a path at the cold-end of the combustion system from a first zone of relative turbulence to a second zone at which the turbulence subsides, said method comprising:adding to the combustion gases at the cold-end of the combustion system and at said zone of turbulence an effective amount for the purpose of an additive consisting essentially of sodium metasilicate such that the additive will travel along with said combustion gases as fine solids or liquid droplets or back from said zone of turbulence to said second zone and will deposit on surfaces of said metal parts, wherein at the point of addition the combustion gases have a temperature of from about 405° F. to about 1000° F.
 2. The method of claim 1, wherein the additive is fed in an amount of from about 0.15 to about 1.0 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 3. The method of claim 2, wherein the additive is fed in an amount of from about 0.25 to about 0.75 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 4. The method of claim 1, wherein the additive is an aqueous solution of sodium metasilicate.
 5. The method of claim 4, wherein the aqueous solution is fed in droplet form to the combustion gases.
 6. The method of claim 5, wherein the additive is fed in an amount of from about 0.15 to about 1.0 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 7. The method of claim 6, wherein the additive is fed in an amount of from about 0.25 to about 0.75 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 8. The method of claim 1, wherein the combustion system is a steam generating system, and wherein the fuel is sulfur-containing oil.
 9. The method of claim 8, wherein the additive is fed in an amount of from about 0.15 to about 1.0 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 10. The method of claim 9, wherein the additive is fed in an amount of from about 0.25 to about 0.75 pound of active sodium metasilicate per pound of sulfur trioxide produced upon combustion of the fuel.
 11. The method of claim 5, wherein the additive is sprayed into the combustion gases.
 12. The method of claim 10, wherein the additive is sprayed into the combustion gases.
 13. The method of claim 3, wherein the additive is sprayed as an aqueous solution in droplet form into the combustion gases.
 14. The method of claim 13, wherein the droplets have a size of about 360 microns or less.
 15. The method of claim 14, wherein the droplets have a size of about 260 microns or less.
 16. The method of claim 15, wherein at the point of addition the combustion gases have a temperature of from about 405° F. to about 650° F.
 17. The method of claim 1, wherein at the point of addition the combustion gases have a temperature of from about 405° F. to about 650° F. 